It was found that lignin β‐O‐4 ketone models could undergo smoothly the hydrogenolysis via light‐induced water‐donating transfer hydrogenation, which provides an example of using inexpensive and eco‐friendly water as the H‐transfer reagent to enable hydrogenolysis of lignin β‐O‐4 ketone models under catalyst‐free condition. Preliminary mechanistic investigations suggest that the mechanistic pathway involves the formation of acetophenone radicals.
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